Anilide carbamates as herbicides

ABSTRACT

New herbicidal m-amidophenyl-N-substituted carbamates.

United States Patent [191 Hill et al.

ANILIDE CARBAMATES AS HERBICIDES Inventors: Kenneth L. Hill, Middleport;

Kenneth R. Wilson, Tonawanda, both of NY.

Assignee: FMC Corporation, New York, NY.

Filed: Sept. 6, 1966 Appl. No.: 577,191

Related US. Application Data Continuation-impart of Ser. No. 496,159,Oct. 14. 1965, abandoned.

References Cited UNITED STATES PATENTS 1/ 1957 Gysin et a1 260/4798/1961 Kaeding 260/479 6/1962 Shulgin 260/479 Dec. 31, 1974 3,091,6335/1963 Strube 260/479 3,099,681 7/ 1963 Kilsheimer et a1 260/4793,110,726 11/1963 Moore et a1. 260/479 3,125,598 3/1964 Kuhle et al.71/111 3,203,949 8/ 1965 Hopkins et a1 71/95 3,226,426 12/1965 Hopkinset al 71/95 3,308,154 3/1967 Schumann 260/479 3,337,608 8/1967 Schumann260/479 3,341,401 9/ 1967 Kilsheimer et a1 260/479 3,362,992 1/1968Schwartz 71/118 3,364,106 1/1968 Kaeding 260/479 FOREIGN PATENTS ORAPPLICATIONS 554,576 3/1958 Canada 260/479 OTHER PUBLICATlONS Gysin etal., Mittle Zur Beeinflussung des Pflanzenwachstums," German Appl. No. G15250, (1956).

Primary ExaminerG1ennon H. Hollrah Attorney, Agent, or Firm-AbnerSheffer; Henry R. Ertelt; Pauline Newman [57] ABSTRACT New herbicidalm-amidophenyl-N-substituted carbamates.

31 Claims, No Drawings ANILIDE CARBAMATES AS HERBICIDES This applicationis a continuation-in-part of out copending application Ser. No. 496,159filed Oct. 14, 1965, now abandoned.

This invention relates to novel herbicidal compounds, to new herbicidalcompositions, and to a new method for the control of undesired plantgrowth, both pre-emergently and post-emergently, by application of saidnew and useful herbicidal compositions.

The novel herbicidal compounds of this invention are m-amidophenylN-substituted carbamates of the following structure:

where is the residue of a primary or secondary amine of the formula Rs vNH, and Bil-o- 32... I

is the residue of a carboxylic acid having at least two carbon atoms ofthe formula R COOH. The substituents R and R may also form aheterocyclic ring with the carbamate nitrogen, e.g. a rnorpholine orpiperidine ring.

In one useful class of compounds, R and R are each aliphatic radicals,more preferably having up to about six catenated carbon atoms, whichaliphatic radicals may be cyclic, straight chain or branched chain,saturated or unsaturated; R is preferably hydrogen but may be loweralkyl group (e.g. methyl).

Examples of R and R aliphatic radicals are methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, isobutyl, tertbutyl, pentyl, neopentyl,isopentyl, l-methylbutyl, 2- methylbutyl, cyclohexyl, cyclopropyl,cyclopentyl, cyclobutyl, hyxyl, l-methylpentyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, l, l, 2, Z-tetramethylpropyl, 1,1- dimethylbutyl,1,1-dimethylpentyl, 1,1,3- trimethylbutyl, l-ethylbutyl, l-ethylpentyl,chloroethyl, 3-chloropropyl, 2-chloropropyl, l-chloro-Z- propyl, ally],l-methylallyl, Z-butenyl, 3-butenyl, 2- propynyl, l-methyl-Z-propynyland, particularly for R vinyl, propenyl, isopropenyl, l-butenyl,l-pentenyl, l-methyl-l-propenyl, 2-methyl-l-propenyl, l-methyll-butenyl,l-methyll -pentenyl, l,3-dimethyl l butenyl, l-ethylvinyl,l-ethyl-l-butenyl, ethynyl, lpropynyl, l-butynyl, and l-chlorobutyl andl-chloro-lmethylbutyl.

Examples of R radicals, other than hydrogen, are methyl, ethyl,isopropyl, propyl and tert-butyl radicals.

In one preferred class of particularly active herbicidal materials R ishydrogen and R l) is the residue of a carboxylic acid in which the alphacarbon atom carries a methyl group. Here K, may be,

for example, ethyl or l-methyl-butyl (which yield especially activeproducts) or tert-butyl, l-methylpentyl or 1,1-dimethylbutyl orisopropyl. In another preferred class, said alpha carbon is part of acyclopropyl ring. In still another preferred class R is a l-propenylradical.

The novel compounds of this invention may be prepared by methodsemployed for the synthesis of carbamates and/or amides. For example,N-monosubstitut- 'ed-carbamic acid esters may be prepared by reacting anappropriate m-amido-phenol with an appropriate isocyanate. This reactionmay be catalyzed by materials such as triethylamine,l,4-diazabicyclo[2.2.2]octane, dibutyltin diacetate, .dimethyltindichloride and dibutylbis (dodecylthio)tin. N,N-Disubstitutedand N-monosubstitutedcarbamic acid esters may be prepared by treating thesodium salt of an appropriate mamidophenol with an N-monosubstitutedorN,N-disubstituted-carbamoyl halide; another name for the1,4-diazabicyclo [2.2.2] octane is triethylenediamine. I

The intermediate m-amidophenols may be prepared by treatment ofm-aminophenol with an acylating agent such as an acyl halide, or an acidanhydride, or an aliphatic acid, to produce a 3'-hydroxyanilide or a 3-hydroxy-N-substituted-anilide. A suitable acid acceptor is used toremove the acid by-product formed in the reaction with an acyl halide oran acid anhydride, and a suitable drying agent is used to remove thewater formed in the reaction with an aliphatic acid.

m-Amidophenyl N-substituted-carbamates may also be prepared by firstconverting an appropriate mamidophenol to its chloroformic acid ester bytreatment with phosgene, then allowing the chloroformate to react with aprimary or secondary amine, including the heterocyclic amines such aspiperidine or morpholine.

Another method useful for the preparation of mamidophenylN-substituted-carbamates involves the treatment of a m-aminophenylN-substitutedor N,N-disubstituted-carbamate with an acyl halide or ananhydride, in the presence of a suitable acid acceptor. Similarly,treatment of the appropriate m-aminophenyl carbamate with an aliphaticacid will produce a mamidophenyl N-substitutedorN,N-disubstitutedcarbamate; this reaction may be driven to completion byremoval of the volatile by-product or water. The intermediatem-aminophenyl N-substituted-or N,N-disubstituted-carbamates may beobtained by reduction of the corresponding m-nitrophenyl carbamateswhich, in turn, may be obtained by treatment of m-nitrophenol with anappropriate isocyanate, or with an N-monosubstitutedorN,N-disubstitutedcarbamoyl halide. Useful m-nitrophenylN-substitutedcarbamates may also be prepared by conversion ofmnitrophenol to its chloroformic acid ester with phospgene and reactionof the m-nitrophenyl chloroformate with a primary or secondary amine.

Other methods useful for the preparation of mamidophenylN-substituted-carbamates include the reaction of a m-amidophenol with analkyl N-substitutedcarbamate or a N-substituted-urea, to yield amamidophenyl N-substituted-carbamate and an alcohol or ammonia, asdescribed in U.S. Pat. No. 2,871,259. In these instances the reactioncan be driven to completion by removal of the volatile by-product.Similarly, the exchange reaction between an aliphatic acid ester of am-amidophenol and an alkyl N-substitutedcarbamate yields a m-amidophenylN-substitutedcarbamate and an aliphatic acid ester; again the reactionmay be driven to completion by removal of the volatile aliphatic acidester.

These reactions of amines with acyl halides, acid anhydrides, acids andamides, and of phenols with phosgene, isocyanates, carbamoyl halides,and other reagents described hereinabove are well known in the art. Forexample, useful procedures for the preparation of carbamic acid estersare described by R. B. Wagner and H. D. Zook, Synthetic OrganicChemistry, Chp. 23, John Wiley and Sons, Inc., New York, 1953. Theacylation of m-aminophenol with acid anhydrides is described by E.Felder and D. Petre, Farmaco (Pavia) Ed. Sci. 15, 60931(l960).

Obviously the reactants selected will depend on the final productdesired, as will the choice of synthetic procedure used. Them-amidophenyl carbamates thus produced are novel compounds, and arecharacterized by excellent herbicidal properties.

For herbicidal applications, the active mamidophenyl carbamates as abovedefined are formulated into herbicidal compositions by admixture, inherbicidally effective amounts, with the adjuvants and carriers normallyemployed for facilitating the dispersion of active ingredients foragricultural applications, recognizing the fact that the formulation andmode of application of a toxicantmay affect the activity of the materialin a given application. Thus, these active herbicidal compounds may beformulated as granulesof relatively large particle size, as wettablepowders, as emulsifiable concentrates, as powdery dusts, as solutions oras any or several other known types of formulations, depending on thedesired mode of application. Preferred formulations for both preandpost-emergence herbicidal applications are wettable powders,emulsifiable concentrates, and granules. These formulations may containas little as 0.5% to as much as 95% or more by weight of activeingredient.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersant. The wettable powder isultimately applied to the soil or foliage as a dry dust or as adispersion in water or other liquid. Typical carriers for wettablepowders include fullers earth, kaolin clays, silicas and other readilywet organic or inorganic diluents. Wettable powders normally areprepared to contain about 5-95% of active ingredient by weight andusually also contain a small amount of a wetting, dispersing oremulsifying agent to facilitate wetting and dispersion. For example, auseful wettable powder formulation contains 80.8 parts by weight of them-amidophenyl carbamate, 17.9 parts by weight of kaolin clay, and 1.0part by weight of sodium lignosulfonate and 0.3 part by weight ofsulfonated aliphatic polyester as wetting agents.

Emulsifiable concentrates are homogeneous liquid compositions which aredispersible in water or other dispersant, and may consist entirely ofthe mamidophenyl carbamate with a liquid or solid emulsifying agent, ormay also contain a liquid carrier, such as xylene, heavy aromaticnaphthas, isophorone and other non-volatile organic solvents. Forherbicidal application these concentrates are dispersed in water orother liquid carrier, and are normally applied as a spray to the area tobe treated. The percentage by weight of the essential active ingredientmay vary according to the manner in which the composition is to beapplied, but in general comprises 0.5 to of active ingredient by weightof the herbicidal composition. For example, a useful emulsifiableconcentrate formulation contains 1 1.6 parts by weight of them-amidophenyl carbamate, 57.7 parts by weight of cresol and 30.7-partsby weight of sulfated ethoxylated nonylphenol.

Granular formulations, wherein the toxicant is carried on relativelycoarse particles, are usually applied without dilution to the area inwhich suppression of vegetation is desired. Typical carriers forgranular formulations include sand, fullers earth, bentonite clays,vermiculite, perlite and other organic or inorganic materials whichabsorb or which may be coated with the toxicant. Granular formulationsnormally are prepared to contain about 5-25% of active ingredient andmay also contain small amounts of other ingredients which may includesurface-active agents such as wetting agents, dispersing agents oremulsifiers; oils such as the heavy aromatic naphthas, kerosene or otherpetroleum fractions, vegetable oils; and/or stickers such as dex trins,glue or synthetic resins. The average particle size of the granules isusually between and 2400 microns. For example, a useful granularformulation contains 5.05 parts byweight of the m-amidophenyl carbamate,5.00 parts by weight of corn oil and 89.95 parts by weight of crushedcorncobs.

Typical wetting, dispersing or emulsifying agents used in agriculturalformulations include, for example, the alkyl and alkylaryl sulfonatesand sulfates and their sodium salts; polyhydric alcohols; and othertypes of surface-active agents, many of which are available in commerce.The surface-active agent, when used, normally comprises from 0.1 to 15%by weight of the herbicidal composition.

Dusts, which are free flowing admixtures of the active ingredient withfinely divided solids such as talc, clays, flours, and other organic andinorganic solids which act as dispersants and carriers for the taxicant,are useful formulations for soil-incorporated applications; the finelydivided solids have an average particle size of less than about 50microns.

Pastes, which are homogeneous suspensions of a finely divided solidtoxicant in a liquid carrier such as water or oil, are employed forspecific purposes. These formulations normally contain about 595% ofactive ingredient by weight, and may also contain small amounts of awetting, dispersing or emulsifying agent to facilitate dispersion. Forapplication, the pastes are normally diluted and applied as a spray tothe area to be affected.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene or other organic solvents. Pressurizedsprays, typically aerosols wherein the active ingredient is dispersed infinely divided form as a result of vaporization 'of a low boilingdispersant solvent carrier, such as the Freons, may alsobe used.

The perparation, properties, and herbicidal activity of representativeherbicidal compounds of this invention are illustrated further in thefollowing examples, in which all temperatures are in degrees Centigrade.

In the following specific examples, which are given to illustrate thisinvention further, references will be made to tests of pre-emergence andpost-emergence herbicidal activity on various plant species. The plantspecies used for the tests were chosen as representative of a broadspectrum of types of plants. In carrying out the tests there were usedflat pans containing, to a depth of three inches, a 1:1 mixture ofsiltloam and sandy-loam soils, and the seeds were planted to the depthindicated for the appropriate plant, taken from the following schedule:

Planting Depth Common Name Scientific Name (inches) Barnyard grassEchinochloa crusgalli V4 1% Carrot Daucus carom V; V; ChickweedCeraslium vulgarum Vi V2 Corn Zea may: 1

Corn cockle Agroslemma Gilhugo V1 V; Cotton Gossypium hirsutum 1Crabgrass Digiraria sanguinalis Vi V Cucumber Cucumis sativus' Vi Curlydock Rumex crispus V4 A Flax Linum usimlissimum Vi A German hay milletSetaria imlica A Va Giant foxtail Selaria magna V4 V2 LambsquarterCherropodium album Vi V2 Lettuce Lactuca saliva /4 /t Lima beanPhaseolus Iimensis l Meadow fescue Festuca elatior Vt b Mustard Brasricajuntea Vi k Oat Avena saliva Vi a Pea Pisum san'vum 1 Peanut Arachishypogaea l Pigweed Amaranlhus relroflexur V1 6 Rice Oryza sativa Vi V;Safflower Carhumus tinclorius Va Vz Soybean Glycine max I Sugar beetBela vulgaris V4 V; Tomato Lycopersicum esrulentum A 9% Velvet leafAbutilon lheop/trarli V4 Medic. Yellow foxtail Semria glauca A V;

For the pre-emergence tests, as soon as the seeds were planted and theflats watered, the toxicant was sprayed on the soil as an acetone-watersolution at the indicated rate. Both the treated flats and the untreatedcontrols were held in the greenhouse for approximately two weeks, afterwhich time the performance of the toxicant was assessed in terms ofpercent kill with respect to the untreated controls.

For the post-emergence tests, the flats were watered and the seedallowed to grow in the greenhouse for approximately two weeks.Maintaining untreated controls,the stand of plants was then sprayed withan aqueous acetone solution of the toxicant at the indicated rate. Aftera period of approximately 2 weeks, the number of surviving plants wasobserved, and the percent kill with respect to the untreated controlswas estimated.

EXAMPLE 1 This example relates to m-(2- methylvaleramido)phenylmethylcarbamate. The intermediate 3-hydroxy-Z-methylvaleranilide wasprepared as follows: 2-Methylvaleryl chloride (13.5 g) was addeddropwise to a solution of m-aminophenol (21.8 g) in 200 ml of dryacetonitrile, maintaining the temperature at 3540. The mixture wasstirred for 2 hours, allowed to stand overnight, and the maminophenolhydrochloride removed by filtration. The filtrate was concentrated todryness under reduced pressure to yield 18 g of3'-hydroxy-Z-methylvaleranilide melting at l37.08.5. This product can berecrystallized from toluene or aqueous methanol.

Analysis: Calculated for C H NO :C 69.54, H 8.27, N 6.76;

Found: C 69.49, H 8.39, N 6.61.

This product was reacted with methyl isocyanate as follows: To a stirredsuspension of 3 hydroxy-2- methylvaleranilide (18.3 g) in 250 ml ofanhydrous ether was added 2 to 3 drops of triethylamine. Methylisocyanate (7.1 g) was added dropwise. and the reaction mixture wasstirred at room temperature overnight. The slurry was then refluxed for6 hours, cooled and filtered. The solid was washed with ether and driedto yield 13.3 g of m-(2-methylvaleramido)phenyl methylcarbamate meltingat 144-5. Evaporation of the filtrate gave an additional 7.0 g of crudeproduct.

Analysis: Calculated for C H N O C 63.61, H 7.63, N 10.60;

Found: C 63.59, H 7.40, N 10.47.

On pre-emergence testing at a dosage of eight pounds per acre, thiscompound showed kill of mustard and flax and severe damage to lettuce,carrots, crabgrass, corn, cotton and lima beans. On post-emergencetesting of this compound at a dosage of 8 pounds per acre there was 100%kill of mustard, lettuce, crabgrass, flax, lima beans, carrots andcotton; corn and oats were so heavily damaged that death was expected.

EXAMPLE 2 This example relates to m-propionamidophenyl methylcarbamate.The intermediate m-aminophenyl methylcarbamate was prepared as follows:Methyl isocyanate (57 g) was added dropwise to a stirred solution ofm-nitrophenol g) and triethylamine (10 drops) in 750 ml of ether and asolution was refluxed for two hours. The product, which precipitated outon cooling, was collected on a filter and washed thoroughly with ether.The crude m-nitrophenyl methylcarbamate was recrystallized from methanolto yield 67 g of solid melting at l335. To a solution of m-nitrophenylmethylcarbamate (156.8 g) in 800 ml of ethyl acetate was added 0.8 g ofplatinum oxide catalyst. The solution was hydrogenated in a Parrhydrogenator. When the theoretical amount of hydrogen had been absorbed,the mixture was filtered to remove the catalyst, and the ethyl acetatewas removed under reduced pressure. The residual oil solidified to yield1 18 g of yellow solid. The crude m-arninophenyl methylcarbamate wasrecrystallized from benzene to melt at 92.5-4.5.

The product was reacted with propionyl chloride as follows: Propionylchloride (7.0 g) was added dropwise to a solution of m-aminophenylmethylcarbamate 12.5 g) and triethylamine (7.0 g) in ml ofbenzene. Themixture was refluxed for 1 hour, cooled and filtered. The solid waswashed thoroughly with water to remove the triethylamine hydrochloride.The residual solid was recrystallized from aqueous methanol to yield 6.7g of m-propionamidophenyl methylcarbamate melting at 156.58.0.

On pre-emergence testing of this compound at a dosage of 4 pounds peracre, 100% of mustard, German hay millet, crabgrass, chickweed andpigweed were killed. On post-emergence testing at a dosage of 4 poundsper acre, 100% of mustard, chickweed, and pigweed and 90% of thecrabgrass were killed; German hay millet and the surviving crabgrassplants were so severely damaged that death appeared likely.

EXAMPLE 3 This example realtes to m-isobutyramidophenyl methylcarbamate.Following the procedure described in Example 2, m-aminophenylmethylcarbamate was reacted with isobutyryl chloride to yieldmisobutyramidophenyl methylcarbamate melting at l62.0-4.5 onrecrystallization from aqueous methanol.

Pre-emergence testing at a dosage of 4 pounds per acre resulted in 100%kill of mustard, chickweed and pigweed, and 90% kill of crabgrass (withthe remaining plants severely damaged and expected to die); the largemajority of German hay millet was also killed. Postemergence testing ata dosage of 4 pounds per acre resulted in 100% kill of pigweed, mustardand chickweed, and moderate damage to German hay millet and crabgrass.

EXAMPLE 4 This example relates to m-(2- methylbutyramido)phenylmethylcarbamate. Following the procedure described in Example 2,maminophenyl methylcarbamate was reacted with 2- methylbutyryl chlorideto yield m-(2- methylbutyramide)phenyl methylcarbamate melting at l61-3on recrystallization from aqueous methanol.

Pre-emergence testing at a dosage of 4 pounds per acre resulting in 100%kill of mustard, chickweed and pigweed, and moderate damage to Germanhay millet and crabgrass. On post-emergence testing a dosage of 4 poundsper acre caused 100% kill of pigweed, and 90% kill of mustard, crabgrassand chickweed, and only slight damage to German hay millet.

EXAMPLE 5 This example relates to m-pivalamidophenyl methylcarbamate.Following the procedure described in Example 2, m-aminophenylmethylcarbamate was reacted with pivaloyl chloride to yieldm-pivalamidophenyl methylcarbamate melting at l79.080.5 onrecrystallization from aqueous methanol.

On pre-emergence testing of this compound a dosage of 4 pounds per acrekilled 100% of mustard, chickweed and pigweed, and caused moderatedamage to German hay millet and crabgrass. On post-emergence testing ata dosage of 4 pounds per acre, 100% of pigweed and chickweed, and themajority of mustard and crabgrass were killed, with only slight damageto German hay millet.

EXAMPLE 6 This example relates to m-crotonamidophenyl methylcarbamate.Following the procedure described in Example 2, m-aminophenylmethylcarbamate was reacted with crotonoyl chloride to yieldmcrotonamidophenyl methylcarbamate melting at 142.0-4.5 onrecrystallization from aqueous methanol.

Pre-emergence testing at a dosage of 4 pounds per acre resulting in 100%kill of mustard, pigweed and chickweed, 90% kill of crabgrass and 80%kill of German hay millet.

EXAMPLE 7 v This example relates to m-(2- methylvaleramido)phenylethylcarbamate. Ethyl isocyanate ml) was added dropwise to a stirredmixture of 3'-hydroxy-2-methylvaleranilide (20.7 g) and triethylamine(15 drops). The reaction mixture was stirred at room temperature for 15minutes, diluted with 100 ml of hexane and filtered. The solid productwas recrystallized from aqueous methanol to yield 22.1 g of m-(2-methylvaleramido)phenyl ethylcarbamate melting at l67-9.

On pre-emergence testing at a dosage of 4 pounds per acre, 100% ofmustard, crabgrass and chickweed were killed, as were 90% of pigweed andof German hay millet. On post-emergence testing at a dosage of4 poundsper acre, 100% of mustard and chickweed were killed, as were ofcrabgrass; German hay millet and pigweed were moderately damaged.

EXAMPLE 8 This example relates to m-(2- methylvaleramido)phenylpropylcarbamate. Following the procedure described in Example7,3'-hydroxy-2- methylvaleranilide was reacted with propyl isocyanate toyield m-(2-methylvaleramido)phenyl propylcarbamate melting at l64.0-5.5on recrystallization from aqueous methanol. v

On pre-emergence testing of this compound at a dosage of 4 pounds peracre, 100% of mustard, pigweed and chickweed, 90% ofGerman hay milletand of crabgrass were killed. Post-emergence testing at a dosage of 4pounds per acre resulted in kill of mustard and chickweed and 50% killof pigweed and crabgrass, with only slight damage to German hay millet.

EXAMPLE 9 This example relates to m-( 2- methylvaleramido)phenylbutylcarbamate. Following the procedure described in Example 7,3-hydroxy-2- methylvaleranilide was reacted with butyl isocyanate toyield m-(2-methylvaleramido)phenyl butylcarbamate melting at l54-6 onrecrystallization 'from aqueous methanol.

Pre-emergence testing of this compound at a dosage of 4 pounds per acreresulted in l00% kill of mustard, chickweed and pigweed, 90% kill ofGerman hay millet and 60% kill of crabgrass. Post-emergence testing at adosage of 4 pounds per acre caused 100% kill of mustard and chickweed,with little or no damage to German hay millet, crabgrass and pigweed.

' EXAMPLE 10 This example relates to m-( 2- methylvaleramido)phenylisopropylcarbamate. Following procedure described in Example 7,3'-hydroxy-2- methylvaleranilide was reacted with isopropyl isocyanateto yield m-(2-methylvaleramido)phenyl isopropylcarbamate melting at l846on recrystallization from aqueous methanol.

Pre-emergence testing of this compound at a dosage of 4 pounds per acreresulted in 100% kill of mustard, lettuce, crabgrass, barnyard grass,chickweed and peanuts, and 75% kill of flax, moderate damage to Germanhay millet, and little or no damage to corn or cotton. Post-emergencetesting at a dosage of 3 pounds per acre resulted in a 100% killof-lettuce and 90% kill of chickweed, moderate damage to mustard andlittle or no damage to German hay millet, barnyard grass and pigweed.

EXAMPLE ll This example relates to m-(2-chloropropionamido)- phenylmethylcarbamate. The intermediate 2-chloro- 3-hydroxypropionanilide(m.p. l57.5-8.5) was prepared from m-aminophenol and 2-chloropropionylchloride following the procedure described in Example 1 for thepreparation of 3'-hydroxy-2- methylvaleranilide.

Following the procedure described in Example 7, 2-ch1oro-3-hydroxypropionanilide was reacted with methyl isocyanate toyield m-(2-chloropropionamido)- phenyl methylcarbamate melting at169.570.5 on recrystallization from aqueous methanol.

On pre-emergence testing of this compound a 4 pound per acre dosagekilled 95% of pigweed and caused moderate damage to mustard, German haymillet, crabgrass and chickweed. Post-emergence testing at a 3 pound peracre dosage resulted in 90% kill of pigweed and 75% kill of lettuce,with little or no damage to mustard, German hay millet, barnyard grassand chickweed.

EXAMPLE 12 This example relates to m-(2,2dimethylvaleramido)- phenylmethylcarbamate. The intermediate 3- hydroxy-2,Ldimethylvaleranilide wasprepared from m-aminophenol and 2,2-dimethylvalery1 chloride followingthe procedure described in Example 1 for the preparation of3'-hydroxy-2methylvaleranilide.

Following the procedure described in Example 7, 3-hydroxy-2,2-dimethylvaleranilide was reacted with methyl isocyanate toyield m-(2,2 -dimethy1- valeramido)phenyl methylcarbamate melting at148.550.5 on recrystallization from aqueous methanol.

Pre'emergence testing of this compound at a dosage of 4 pounds per acreresulted in 100% kill of mustard and pigweed, 95% kill of chickweed, 90%kill of crabgrass and 75% kill of German hay millet. Postemergencetesting of this compound at a dosage of 3 pounds per acre resulted in100% kill of mustard, lettuce and chickweed, with slight to moderatedamage to German hay millet, barnyard grass and pigweed.

EXAMPLE 13 This example relates to m-methacrylamidophenylmethylcarbamate. The intermediate 3-hydroxymethacrylanilide was preparedas follows: Methacryloyl chloride (15.7 g) was added dropwise to asolution of maminophenol (32.7 g) in 150 ml of acetonitrile, maintainingthe temperature at 3540. The mixture was stirred for 2 hours, allowed tostand overnight and filtered. The solid was washed thoroughly with waterto remove the m-aminophenol hydrochloride, and recrystallized fromaqueous methanol to yield 17.5 g of 3'-hydroxymethacrylanilide meltingat 17880.

Following the procedure described in Example 7,3'-hydroxymethacry1anilide was reacted with methyl isocyanate to yieldm-methacrylamidophenyl methylcarbamate melting at 179-82 onrecrystallization from methanol.

Pre-emergence testing of this compound at a dosage of 4 pounds per acreresulted in 90% kill of mustard and pigweed, 70% kill of chickweed and50% kill German hay millet, with moderate damage to crabgrass and thesurviving plants of the aforementioned species. Post-emergence testingof this compound at a dosage of 3 pounds per acre resulted in 100% killof lettuce and slight to moderate damage to mustard, German hay millet,barnyard grass, chickweed and pigweed.

EXAMPLE 14 This example relates to m-(2-methyl-2- pentenamido)phenylmethylcarbamate. The intermediate 3-hydroxy-2-methyl-2-pentenanilide(crude m.p. 6976) was prepared from m-aminophenol andZ-methyI-Z-pentenoyl chloride following the procedure described inExample 1 for the preparation of 3- hydroxy-2-methylvaleranilide.

Following the procedure described in Example 7, crude3'-hydroxy-2-methyl-2-pentenanilide was reacted with methyl isocyanateto yield m-(2-methyl-2- pentenamido)phenyl methylcarbamate melting at166- 9 on recrystallization from aqueous methanol.

Pre-emergence testing of this compound at a dosage of 4 pounds per acreresulted in 100% kill of mustard, chickweed, and pigweed, 50% kill ofGerman hay millet and 40% kill of crabgrass with moderate damage to thesurviving plants. Postemergence testing ofthis compound at a dosage ofSpounds per acre resulted in 100 kill of mustard, lettuce, chickweed,and pigweed, moderate damage to bannyard grass, but no injury to Germanhay millet.

EXAMPLE 15 This example relates to m-(Z- methylva1eramido)phenyldimethylcarbamate. To a stirred suspension of sodium hydride (2.7 g) in100 ml of 1,2-dimethoxyethane, a solution of 3'-hydroxy-2-methylvaleranilide (20.7 g) in 50 ml of 1,2- dimethoxyethane was addeddropwise. When the addition was complete and the evolution of hydrogenhad ceased, the slurry was stirred at room temperature for one-halfhour. Dimethylcarbamoyl chloride (11.9 g) was then added dropwise andthe mixture was allowed to stir overnight. The precipitated sodiumchloride was removed by filtration and the filtrate was concentratedunder reduced pressure to a yellow oil which crystallized on triturationwith hexane to melt at 83.56.5. Recrystallization from benzene-hexanegave 17.5 g of m-(2-methylvaleramido)phenyl dimethylcarbamate, meltingat 84.57.0.

Pre-emergence testing of this compound at a dosage of 4 pounds per acreresulted in 100% kill of mustard, German hay millet and pigweed, andkill of chickweed, and moderate damage to crabgrass. Postemergencetesting of this compound at a dosage of 3 pounds per acre resulted inkill of lettuce and chickweed, and 75% kill of mustard, with little orno damage to German hay millet, barnyard grass and pigweed.

EXAMPLE 16 This example relates to m-( 2- methylvaleramido)phenyltert-butylcarbamate. tert- Butyl isocyanate (5.1 g) was added to amixture of 3'- hydroxy-2-methylvaleranilide (10.0 g) and triethylamine(5 drops). The reactants were mixed thoroughly by hand, and the flaskwas stoppered and heated in a water bath at 50 for 2 hours. The crudeproduct was recrystallized from aqueous ethanol to yield 6.2 g of M-(Z-methylvaleramido)phenyl tert-butylcarbamate melting at 1524. A secondrecrystallization from aqueous ethanol raised the melting point to153-4.

Analysis: Calculated for C l-l N O C 65.72. H 8.27, N 9.58;

Found: C 65.61, H 8.05, N 9.25.

The same product can be obtained using 1,4- diazobicyclo-[2.2.2]octaneor dibutyltin diacetate as a catalyst in place of the triethylamine.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce and chickweed, 95% kill ofGerman hay millet and 90% kill of barnyard grass and pigweed.Postemergence testing of this compound at a dosage of 3 pounds per acreresulted in 100% kill of mustard, lettuce and chickweed and slight tomoderate damage to German hay millet, barnyard grass and pigweed.

EXAMPLE 17 This example relates to m-acetamidophenyl methylcarbamate.Following the procedure described inExample l, a solution of3-hydroxyacetanilide in dioxane was reacted with methyl isocyanate inthe presence of triethylamine catalyst. The m-acetamidophenylmethylcarbamate melted at l57.08.5 after recrystallization from ethanol.

Post-emergence testing of this compound at a dosage of 8 pounds per acreresulted in 100% kill of lettuce and 50% kill of mustard (with thesurviving plants so badly damaged that their death appeared likely),Without severe damage to lima beans, corn, cotton, crabgrass, flax,carrots and oats.

EXAMPLE 18 This example relates to m-propionamidophenyltertbutylcarbamate. The intermediate 3-hydroxypropionanilide (m.p.180-1) was prepared from maminophenol and propionyl chloride followingthe procedure described in Example l for the preparation of 3'-hydroxy-Z-methylvaleranilide.

3'-Hydroxypropionanilide (16.5 g) was placed in a flask withtriethylenediamine (1.12 g) and treated with 9.9 g of tert-butylisocyanate. The reaction was stirred well and heated for 2 hours.Recrystallization from ethanol gave 10.4 g of m-propionamidophenyltertbutylcarbamate melting at l778.

Analysis: Calcd for C I-1 N C 63.61, H 7.63, N 10.60;

Found: C 63.34, H 7.71, N 10.40.

In both preand postemergence testing of this compound, a dosage of 6pounds per acre resulted in 100% kill of mustard, lettuce, German haymillet, barnyard grass, chickweed and pigweed. 1

EXAMPLE 19 This example relates to m-propionamidophenylisopropylcarbamate. Following the procedure described in Example 7,3-hydroxypropionanilide was reacted with isopropyl isocyanate andtriethylamine to yield mpropionamidophenyl isopropylcarbamate melting at173.5 on recrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce, German hay millet, barnyardgrass, chickweed and pigweed. In a post-emergence test on mustard,lettuce, German hay millet, crabgrass, flax and chickweed at a dosage of6 pounds per acre, there was 100% kill of all species.

EXAMPLE 20 This example relates to m-propionamidophenylisobutylcarbamate. Following the procedure described in Example 18,3'-hydroxypropionanilide was reacted with isobutyl isocyanate andtriethylenediamine to yield m-propionamidophenyl isobutylcarbamatemelt-, ing at l7l.5-2.5 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, and kill of lettuce and flax,respectively, with the remaining plants not expected to live, andmoderate damage of crabgrass. Post-emergence testing of this compound ata dosage of 6 pounds per acre'resulted in kill of mustard and lettuce,95% kill of carrots. 60% kill of flax, and moderate control ofcrabgrass.

EXAMPLE 21 This example relates to m-propionamidophenylsecbutylcarbamate. Following the procedure described in Example 18,3'-hydroxypropionanilide was reacted with sec-butyl isocyanate andtriethylenediamine to yield m-propionamidophenyl sec-butylcarbamatemelting at 174-6 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and flax, 90% kill of lettuce withsevere injury to the surviving plants, and 95% kill of crabgrass withthe remaining plants not expected to survive. Postemergen'ce testing ofthis compound at a dosage of 6 pounds per acre resulted in 100% kill ofmustard, flax, carrots and lettuce, and 95% kill of crabgrass withmoderate injury to the surviving plants.

. EXAMPLE 22 The example relatesto m-(propionamido)phenylallylcarbamate. Following the procedure described in Example 7,3'-hydroxypropionanilide was reacted with allyl isocyanate andtriethylamine to yield m- (propionamido)phenyl allylcarbamate melting at6 on recrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, German hay millet, flax, carrots andcrabgrass, and 95% kill of lettuce with severe injury to survivingplants. Post-emergence testing of this compound at a dosage of 6 poundsper acre resulted in 100% kill of mustard, lettuce, German hay millet,flax, carrots, and crabgrass.

EXAMPLE 23 The example relates to m-propionamidophenyl(2-chloroethyl)-carbamate. Following the procedure described in Example7, 3-hydroxypropionanilide was reacted with 2-chloroethyl isocyanate andtriethylamine to yield m-propionamidophenyl (2-chloroethyl) carbamatemelting at 6 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and lettuce, 95% kill of flax, 80% killof barnyard grass, 70% kill of German hay millet, and 60% kill ofcrabgrass. In all cases of partial kill, the surviving plants wereseverely injured. Post-emergence testing of this compound at a dosage of6 pounds per acre resulted in 100% kill of mustard, lettuce, crabgrass,German hay millet, flax and barnyard grass.

EXAMPLE 24 This example relates to m-propionamidophenylcyclohexylcarbamate. Following the procedure described in Example 18,3-hydroxypropionanilide was reacted with cyclohexyl isocyanate anadtriethylenediamine to yield m-propionamidophenyl cyclohexylcarbamatemelting at l8l2.5 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acregave the following results: 100% kill of mustard, 95% kill of lettucewith severe injury to the surviving plants, moderate damage to flax,barnyard grass and crabgrass and only slight damage to German haymillet. Post-emergence testing of this compound at a dosage of 6 poundsper acre resulted in 100% kill of mustard'and lettuce, 95% kill of flaxwith remaining plants expected to die, and little or no effect oncrabgrass and German hay millet.

EXAMPLE 25 This example relates to m-propionamidophenylN,N-dimethylcarbamate. The intermediate sodium salt of3'-hydroxypropionanilide was prepared by reacting3-hydroxypropionanilide (165 g) with methanolic so dium methoxide(obtained by dissolving sodium metal (23 g) in 1800 ml methanol). Thesolution was stirred for 1 hour at room temperature. Evaporation of themethanol left a sticky solid which was washed twice with benzene.Evaporation of the benzene left 123.4 g of the desired intermediatemelting at 67-9.

Dimethylcarbamoyl chloride (10.8 g, 0.1 mole) was added dropwise to aslurry of the sodium salt of 3-hydroxypropionanilide (18.7 g, 0.1 mole)in 150 ml of acetonitrile. The mixture was stirred for 12 hrs, thenfiltered to recover 5.1 g (87%) of sodium chloride. The solvent wasremoved from the filtrate in vacuo to give 21.7 g of a dark oil whichcrystallized on standing, m.p. 905. Recrystallization from ethanol-watergave a white solid, mp. 99-100.

Analysis: Calcd for C H N O C 61.00, H 6.83, N l 1.86;

Found: C 60.87, H 6.71, N 11.96.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and flax, 95% kill of lettuce withsevere damage to the surviving plants, 90% kill of German hay milletwith severe damage to the surviving plants and severe damage to barnyardgrass and crabgrass. Post-emergence testing of this compound at a dosageof 6 pounds per acre resulted in 100% kill of mustard, lettuce,crabgrass, flax and German hay millet, and 95% kill of barnyard grasswith the remaining plants not expected to survive.

EXAMPLE 26 This example relates to m-propionamidophenyl ethylcarbamate.Following the procedure described in Example 7, 3-hydroxypropionanilidewas reacted with ethyl isocyanate and triethylamine to yieldmpropionamidophenyl ethylcarbamate melting at l689 on recrystallizationfrom aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, crabgrass, flax, German hay millet andbarnyard grass, and 95% kill of lettuce with severe injury to survivingplants. Post-emergence testing of this compound at a dosage of 6 poundsper acre resulted in 100% kill of mustard, lettuce, crabgrass, flax,barnyard grass and German hay millet.

EXAMPLE 27 This example relates to m-propionamidophenyl propylcarbamate.Following the procedure described in Example 7, 3-hydroxypropionanilidewas reacted with propyl isocyanate and triethylamine to yieldmpropionamidophenyl propylcarbamate melting at 157-8 onrecrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in l00% kill of mustard, lettuce, flax and German hay millet,and kill of crabgrass and barnyard grass with severe injury to thesurviving plants. Post-emergence testing of this compound at a dosage of6 pounds per acre resulted in 100% kill of mustard, lettuce, crabgrass.barnyard grass, flax and German hay millet.

EXAMPLE 28 This example relates to m-propionamidophenyl hexylcarbamate.Following the procedure described in Example 7, 3-hydroxypropionanilidewas reacted with hexyl isocyanate and triethylamine to yieldmpropionamidophenyl hexylcarbamate melting at l40.0-0.5 onrecrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and kill of lettuce with the remainingplants not expected to survive, while German hay millet, crabgrass,barnyard grass and flax were undamaged. Postemergence testing of thiscompound at a dosage of 6 pounds per acre resulted in kill of mustardand lettuce with little or no damage to flax, German hay millet,crabgrass and barnyard grass.

EXAMPLE 29 This example relates to m-propionamidophenyl 1,13,3-tetramethylbutylcarbamate. Following the procedure of Example 18,3-hydroxypropionanilide was reacted with l,l,3,3-tetramethylbutylisocyanate and triethylenediamine to yield m-propionamidophenyl 1,1,3-,3-tetramethylbutylcarbamate melting at l356 on recrystallization fromaqueous ethanol.

Pre-emergence and post-emergence testing of this compound at a dosage of6 pounds per acre resulted in 100% kill of mustard, lettuce and flax,while German hay millet, crabgrass and barnyard grass were undamaged.

EXAMPLE 30 This example relates to m-propionamidophenyldiisopropylcarbamate. The intermediate sodium salt of3'-hydroxypropionanilide was prepared in the manner described in Example25. Following the procedure used in the same example, this sodium saltwas reacted with diisopropyl carbamoyl chloride to yieldmpropionamidophenyl diisopropylcarbamate melting at l25.5-7.0 onrecrystallization from aqueous methanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce, flax and German hay millet,90% kill of crabgrass with moderate damage to the surviving plants andmoderate control of barnyard grass. Post-emergence testing of thiscompound at a dosage of 6 pounds per acre resulted in 100% kill ofmustard and lettuce, 80% kill ofcrabgrass with moderate damage to thesurviving plants and moderate control of German hay millet.

EXAMPLE 31 This example relates to m-propionamidophenyl diethylcarbamate. Following the procedure of Example 25 the sodium salt of3'-hydroxypropionanilide was reacted with diethyl carbamoyl chloride toyield mpropionamidophenyl diethylcarbamate melting at 856 onrecrystallization from aqueous ethanol.

Pre-emergence testing with this compound at a dos age of 6 pounds peracre resulted in 100% kill of mustard, barnyard grass, flax and Germanhay millet, 90% kill of lettuce with moderate injury to the survivingplants, and 80% kill of crabgrass with moderate injury to the survivingplants. Post-emergence testing of this compound at a dosage of 6 poundsper acre resulted in 100% kill of mustard, lettuce, crabgrass, barnyardgrass, flax and German hay millet.

EXAMPLE 32 This example relates to m-isobutyramidophenylisopropylcarbamate. The intermediate 3- hydroxyisobutyranilide (m.p.l80-l) was prepared from m-aminophenol and isobutyl chloride followingthe procedure described in Example 1 for the preparation of3'-hydroxy-2-methylvaleranilide. Following the procedure described inExample 7, 3- hydroxyisobutyranilide was reacted with isopropylisocyanate and triethylamine to yield misobutyramidophenylisopropylcarbamate melting at l79-l80 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of lettuce, 90% kill of mustard and 95% kill ofchickweed with moderate injury to the remaining plants in both cases,50% kill of pigweed, and moderate damage to German hay millet andbarnyard grass. Post-emergence testing of this compound at a dosage of 6pounds per acre resulted in 50% kill of lettuce with moderate injury tosurviving plants and moderate injury to mustard, barnyard grass,chickweed and pigweed, with slight damage to German hay millet.

EXAMPLE 33 grass and moderate damage to German hay millet.

Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of chickweed, 95 and 75% kill of mustard andlettuce, respectively, with the remaining plants expected to die, andmoderate damage to barnyard grass and pigweed.

EXAMPLE 34 The example relates to m-crotonamidophenylisopropylcarbamate. The intermediate 3 hydroxycrotonanilide (m.p. l63-4)was prepared from m-aminophenol and crotonyl chloride following theprocedure described in Example I for the preparation of3'-hydroxy-2-methylvaleranilide. Following the procedure described inExample 18, 3- hydroxycrotonanilide was reacted with isopropylisocyanate and triethylamine to yield m-crotonamidophenylisopropylcarbamate which melted at l734 on recrystallization fromaqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard.

.lettuce, and chickweed, 95% kill of German hay millet.

with remaining plants expected to die. moderate damage to barnyard grassand slight damage to pigweed. Post-emergence testing of this compound ata dosage of 8 pounds per acre resulted in 100% kill of mustard, lettuce,crabgrass, corn and lima beans.

EXAMPLE 35 This example relates to m-crotonamidophenyltertbutylcarbamate. Following the procedure described in Example 18,3-hydroxycrotonanilide was reacted with tert-butyl isocyanate andtriethylenediamine to yield m-crotonamidophenyl tert-butylcarbamatemelting at 2078 on recrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce, chickweed and pigweed, 95%kill of German hay millet with moderate damage to surviving plants, andkill of barnyard grass with moderate injury to surviving plants.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce, German hay millet andchickweed, and kill of crabgrass with moderate injury to the remainingplants, and moderate damage to flax.

EXAMPLE 36 This example relates to m-crotonamidophenyl ethylcarbamate.Following the procedure described in Example 7, 3'-hydroxycrotonanilidewas reacted with ethyl isocyanate and triethylamine to yieldmcrotonamidophenyl ethylcarbamate melting at 1478 on recrystallizationfrom aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in kill of mustard, lettuce, flax and German hay millet, 90%kill of crabgrass with severe injury to the surviving plants, and 80%kill of barnyard grass with the remaining plants not expected to live.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, flax and lettuce, 90% kill of barnyardgrass with the remaining plants not expected to live, 80% kill of Germanhay millet with the remaining plants not expected to live and 50% killof crabgrass with moderate damage to surviving plants.

EXAMPLE 37 This example relates to m-crotonamidophen'yl propylcarbamate.Following the procedure described in Example 7, 3-hydroxycrotonanilidewas reacted with propyl isocyanate and triethylamine to yieldmcrotonamidophenyl propylcarbamate melting at l678 on recrystallizationfrom ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, crabgrass, lettuce and flax, 70% killof German hay millet with moderate damage to surviving plants andmoderate damage to barnyard grass. Post-emergence testing of thiscompound at a dosage of 6 pounds per acre resulted in 100% kill ofmustard and lettuce, 75% kill of German hay millet with moderate damageto surviving plants, 50% kill of crabgrass with moderate damage tosurviving plants, slight control of barnyard grass and 80% kill of flaxwith the remaining plants expected to die.

EXAMPLE 38 This example relates to m-crotonamidophenyl allylcarbamate.Following the procedure described in Example 7, 3-hydroxycrotonanilidewas reacted with allyl isocyanate and triethylamine to yieldmcrotonamidophenyl allylcarbamate melting at 150-l on recrystallizationfrom ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce and flax, 90% kill ofcrabgrass with severe injury to surviving plants, 90% kill of German haymillet with the remaining plants expected to die, 70% kill of barnyardgrass with moderate injury to surviving plants. Post-emergence testingof this compound at a dosage of 6 pounds per acre resulted in 100% killof mustard, lettuce and barnyard grass, 75% kill of German hay milletwith remaining plants not expected to live, 60% kill of crabgrass withmoderate damage to the surviving plants, and 60% kill of flax with theremaining plants expected to die.

EXAMPLE 39 This example relates to m-crotonamidophenylsecbutylcarbamate. Following the procedure described in Example 18,3-hydroxycrotonanilide was reacted with sec-butyl isocyanate andtriethylenediamine to yield m-crotonamidophenyl sec-butylcarbamatemelting at l989 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and flax, 95% kill of lettuce withsevere injury to the surviving plants, 90% kill of crabgrass withmoderate injury to the surviving plants, 80% kill of German hay milletwith moderate damage to the surviving plants and moderate damage tobarnyard grass. Postemergence testing of this compound at a dosage of 6pounds per acre resulted in 100% kill of mustard, lettuce and flax, 80%kill of German hay millet with the remaining plants not expected tolive, and moderate control of crabgrass.

EXAMPLE 40 This example relates to m-crotonamidophenyldimethylcarbamate. A mixture of triethylamine (7.3 g), 125 ml of benzeneand maminophenyl dimethylcarbamate (13.0 g) was treated cautiously withcrotonyl chloride (7.5 g) maintaining the temperature at ca 60. Thereaction was stirred at 60 for 3 hours, cooled and filtered. Thefiltrate was chilled to 60C, washed with cold 5% HC] and water, thendried over MgSO The dried benzene solution was treated twice withactivated charcoal, the benzene removed by evaporation and the crude oilrecrystallized from water to yield mcrotonamidophenyl dimethylcarbamatemelting at 90-1.

Analysis: Calcd for C, H, N O C 62.80, H 6.50, N l 1.28;

Found: C 63.01, H 6.57, N 11.19.

Pre-emergence testing of this compound at a dosage of6 pounds per acreresulted in 50% kill of lettuce with moderate damage to surviving plantsand moderate control of mustard, crabgrass and German hay millet withlittle effect on barnyard grass. Post-emergence testing of this compoundat a dosage of 6 pounds per acre resulted in 100% kill of mustard, 60%kill of lettuce with moderate damage to the surviving plants and slightcontrol of crabgrass, with little effect on German hay millet andbarnyard grass.

EXAMPLE 41 This example relates to m-butyramidophenyl methylcarbamate.The intermediate 3-hydroxybutyranilide (m.p. 1366.5) was prepared fromm-aminophenol and butyryl chloride following the procedure described inExample 1 for the preparation of 3-hydroxy2- methylvaleranilide.Following the procedure described in Example 7, 3-hydroxybutyranilidewas reacted with methyl isocyanate and triethylamine to yieldmbutyramidophenyl methylcarbamate melting at 1489 on recrystallizationfrom ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce, chickweed and pigweed and 40%kill of German hay millet with moderate damage to the surviving plants.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce and chickweed, kill of pigweedwith moderate injury to surviving plants and some kill of German haymillet and barnyard grass.

EXAMPLE 42 This example relates to m-valeramidophenyl methylcarbamate.The intermediate 3-hydroxyvaleranilide (m.p. l l56) was prepared fromm-aminophenol and valeryl chloridefollowing the procedure described inExample 1 for the preparation of 3'-hydroxy-2- methylvaleranilide.Following the procedure described in Example 7, 3-hydroxyvaleranilidewas reacted with methyl isocyanate and triethylamine to yield m-(valeramido)phenyl methylcarbamate melting at l40l on recrystallizationfrom ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and chickweed and kill of lettuce withmoderate damage to the surviving plants; German hay millet and barnyardgrass were unaffected and pigweed was only slightly affected.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 95% kill of chickweed and 90% kill of mustard with moderatedamage to the surviving plants in both cases; German hay millet,barnyard grass and pigweed were unaffected and lettuce was only slightlyaffected.

EXAMPLE 43 This example relates to m-hexanamidophenyl methylcarbamate.The intermediate 3-hydroxyhexanilide (mp. l35-6) was prepared fromm-aminophenol and hexanoyl chloride following the procedure described inExample 1 for the preparation of 3-hydroxy-2- methylvaleranilide.Following the procedure described in Example 7, 3'-hydroxyhexanilide wasreacted with methyl isocyanate and triethylamine to yieldmhexanamidophenyl methylcarbamate melting at l38-9 on recrystallizationfrom aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 90% kill of mustard and chickweed with moderate injury tosurviving plants, while lettuce and pigweed were only slightly affectedand German hay millet and barnyard grass were unaffected. Post-emergencetesting of this compound at a dosage of 6 pounds per acre resulted in100% kill of mustard and 80% kill of chickweed with moderate damage tothe surviving plants, while lettuce, German hay millet, crabgrass andpigweed were unaffected.

EXAMPLE 44 This example relates to m-(2,2-dimethylbutyramido)-phenylmethylcarbamate. The intermediate 3'-hydroxy-2,2-dimethylbutyranilide(m.p. 944.5) was prepared from m-aminophenol and 2,2-dimethylbutyrylchloride following the procedure I described in Example 1 for thepreparation of 3'- hydroxy-2-methylvaleranilide. Following the proceduredescribed in Example 7, 3'-hydroxy-2,2- dimethylbutyranilide was reactedwith methyl isocyanate and triethylamine to yieldm-(2,2-dimethylbutyramido)phenyl methylcarbamate melting at 150l onrecrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and chickweed and 95% kill of lettucewith the surviving plants not expected to live, and 75% kill of pigweedwith moderate damage to the surviving plants; German hay millet wasmoderately damaged and barnyard grass was only slightly damaged.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 75% kill of mustard and lettuce with moderate injury to thesurviving plants and 50% kill of pigweed with moderate damage tosurviving plants and moderate control of chickweed, while barnyard grasswas unaffected.

EXAMPLE 45 This example relates to m-(2- methylcrotonamido)phenylmethylcarbamate. The intermediate 3'-hydroxy-2-methyl-crotonanilide(m.p. l58.5-9) was prepared following the procedure described in Example1 for the preparation of 3'-hydroxy- 2-methylvaleranilide. Following theprocedure described in Example 18, 3 '-hydroxy-2- methylcrotonanilidewas reacted with methyl isocyanate and triethylamine to yield m-(2-methylcrotonamido)phenyl methylcarbamate which melted at 1556.5 onrecrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce and chickweed, 80% and 95%kill of German hay millet and barnyard grass, respectively, withmoderate damage to the surviving plants as well as moderate control ofpigweed. Post-emergence testing of this compound at a dosage of 6 poundsper acre resulted in 100% kill of mustard and chickweed, 80% and 75%kill of barnyard grass and lettuce, respectively, with moderate damageto surviving plants and moderate control of pigweed.

EXAMPLE 46 This example relates to m-(2-chloro-2-methylvaleramido)-phenyl methylcarbamate. The intermediate phenol wasprepared as follows: 65.5 g of m aminophenol was dissolved in 400 mlacetonitrile at 40. To this solution was added dropwise 50.7 g of2-chloro-2-methylvaleroyl chloride while the temperature was maintainedbelow 55. The mixture was poured into two liters of crushed ice. The oilwhich separated was washed with 10% sodium bicarbonate solution, 10%hydrochloric acid and finally with water. The washed oil was dissolvedin hot hexane, the solution treated 3 times with activated charcoal andthe hexane removed under reduced pressure to leave 2-chloro-3-hydroxy-2-methylvaleranilide, which did not crystallize. Following theprocedure described in Example 7,2-chloro-3-hydroxy-2-methylvaleranilide was reacted with methylisocyanate and triethylamine to yield m-(2-chloro-2-methylvaleramido)phenyl methylcarbamate which melted at 1456when recrystallized from ethanol.

Analysis: Calcd for C H ClN O C 56.57, H 6.44. N, 9.41, Cl11.94

Found: C 56.43, H 6.40, N 9.26, Cl 11.79

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and chickweed, 90% kill of pigweed withmoderate damage to the surviving plants, 80% kill of lettuce with severeinjury to surviving plants, kill of German hay millet with moderatedamage to surviving plants, and moderate damage to barnyard grass.Postemergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard and lettuce, and slight to moderatedamage to German hay millet and pigweed.

' EXAMPLE 47 This example relates to A m-( 2- methylvaleramido)phenylisobutylcarbamate. The intermediate 3 '--hydroxy-2-methyl-valeranilide(l37.08.5) was prepared from m-aminophenol and 2-methylvaleryl chloridefollowing the procedure described in Example 1 for the preparation ofthis same intermediate. Following the procedure described in Example 18,3-hydroxy-Z-methylvaleranilide was reacted with isobutyl isocyanate andtriethylenediamine to yield m-(2-methylvaleramido)phenylisobutylcarbamate melting at l56-7 on recrystallization from aqueousethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce and chickweed, 95% kill ofpigweed, kill of barnyard grass and 60% kill of German hay millet.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, kill of lettuce with surviving plantsnot expected to live, 50% kill of chickweed with slight injury to thesurviving plants and moderate control of German hay millet; flax wasslightly damaged and crabgrass was unaffected.

EXAMPLE 48 This example relates to m-( 2- methylvaleramido )phenylallylcarbamate. Following the procedure described in Example 7,3-hydroxy-2- methylvaleranilide was reacted with allyl isocyanate andtriethylamine to yield m-(2-methylvaleramido)- phenyl allylcarbamatemelting at l49.09.5 on recrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of6 pounds per acreresulted in a kill of mustard, lettuce, German hay millet and flax, 95%kill of crabgrass with moderate injury to the surviving plants andmoderate control of barnyard grass. Post-emergence testing of thiscompound at a dosage of 6 pounds per acre resulted in 100% kill-ofmustard and lettuce and 90% kill of barnyard grass and flax with theremaining plants not expected to survive; German hay millet andcrabgrass were moderately damaged.

EXAMPLE 49 This example relates to m-(2- met-hylvaleramido)phenyldiisopropylcarbamate. Diisopropylcarbamoyl chloride (16.4 g) was addeddropwise to a slurry of the sodium salt of 3- hydroxyvaleranilide (22.9g) prepared by the method of Example 25, in 250 ml of acetonitrile. Themixture was stirred for 21 hours and filtered to recover 5.2 g of sodiumchloride. The solvent was removed from the filtrate in vacuo to give23.4 g of a light yellow oil, confirmed by analysis to be m-(2-methylvaleramido)phenyl diisopropylcarbamate b.p. 133 at 5 X 105mm. Hg.Analysis: Calcd for C, H N O C 68.23, H 9.04, N 8.38

Found: C 68.36, H 8.94, N 8.20.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, 90% kill of lettuce and German haymillet with moderate damage to the surviving plants, 95% kill ofcrabgrass with the remaining plants not expected to live and 80% kill offlax with moderate damage to surviving plants; barnyard grass was onlyslightly affected. Postemergence testing of this compound at a dosage of6 pounds per acre resulted in 90% kill of mustard with the remainingplants not expected to survive, 75% kill of lettuce with moderate damageto the surviving plants and moderate damage to flax; German hay millet,crabgrass and barnyard grass were unaffected.

EXAMPLE 50 This example relates to m-[2- cyclopropylacetamido]phenyltert-butylcarbamate. A mixture of 3-hydroxy-2-cyclopropylacetanilide(10.7 g), triethylamine (9 g) and tert'butyl isocyanate (6 g) in 50 mlof dimethylformamide was heated at 70 for 24 hours. The solution wascooled to room tempera ture,f1ltered and poured into 400 ml of coldwater. The solid which separated was isolated and found identical tothat separated initially. Recrystallization of the combined solids fromaqueous ethanol gave 8.6 g of m-[2- cyclopropylacetamido]phenyltert-butylcarbamate, m.p. 2l3.0-213.5.

Analysis: Calcd for C H N O C 65.19, H 7.30, N

Found: C 65.15, H 7.06, N 10.19.

Both pre-emergence and post-emergence testing of this compound at adosage of 6 pounds per acre resulted in 100% kill of mustard, lettuce,crabgrass, barnyard grass, German hay millet and flax.

EXAMPLE 51 This example relates to m-(2- methylvaleramido)phenylsec-butylcarbamate. Following the procedure described in Example 18, 3'-hydroxy-2-methylvaleranilide was reacted with sechutylcarbamate meltingat 172-4 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, 70% killof flax, and moderate controlof lettuce and crabgrass. Post-emergence testing of this compound at adosage of 6 pounds per acre resulted in moderate control of mustard andcrabgrass, 50% kill of flax and slight damage to carrots.

EXAMPLE 52 This example relates to m-(2- chlorovaleramido)phenylmethylcarbamate. The intermediate 2-chloro-3-hydroxyva|eranilide, m.p.l20.0-121.5, was prepared from m-aminophenol and 2-chlorovaleroylchloride by the procedure described in Example 1 for the preparation of3-hydrox \'-Z- methylvaleranilide.

Analysis: Calcd for C H ClNO C 58.02. H 6.16. N 6.15, C] 15.62

Found: C 58.37, H 6.34, N 618, C1 14.19 Following the procedure ofExample 7, 2-chloro-3- hydroxyvaleranilide was reacted with methylisocyanate to yield m-(2-chlorovaleramido)phenyl methylcarbamate, whichmelted at 143.0-144.5 on recrystallization from aqueous ethanol.

Analysis: Calcd for C T-I CIN O C 54.83, H 6.01,

Found: C 54.62, H 5.74, N 9.62

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce, crabgrass and chickweed and90 and 60% kill of flat and German hay millet, respectively, withmoderate damage to the surviving plants. Post-emergence testing of thiscompound at 6 pounds per acre resulted in 100% kill of lettuce andcrabgrass, 95% kill of mustard with moderate injury to surviving plants,95% kill of German hay millet with the remaining plants expected to die,kill of chickweed, and kill of flax.

EXAMPLE 53 This example relates to m-(2,2-dimethylvaleramido) phenylisopropylcarbamate. The intermediate 3- hydroxy-2,2-dimethylvaleranilidewas prepared from m-aminophenol and 2,2-dirnethylvaleryl chloridefollowing the procedure described in Example'46. Again the oil did notcrystallize.

Analysis: Calcd for C H NO C 70.55, H 8.65;

Found: C 70.85, H 8.56.

Following the procedure described in Example 7, the intermediate wasreacted with isopropyl isocyanate and triethylenediamine to yieldm-(2,2-dimethylvaleramido)phenyl isopropylcarbamate melting at 140l onrecrystallization from aqueous ethanol. Analysis: Calcd for C H N O C66.64, H 8.55, N 9.14;

Found: C 66.51, H 8.68, N 9.03.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, flax and lettuce and kill of crabgrasswith moderate injury to the surviving plants. Post-emergence testing ofthis compound at a dosage of 6 pounds per acre resulted in kill ofmustard, flax and lettuce and 90 and 70% kill of carrots and crabgrass,respectively, with moderate injury to the surviving plants.

EXAMPLE 54 This example relates to m-(2,2-dimethylvaleramido)- phenyltert-butylcarbamate. Following the procedure described in Example 18,3-hydroxy-2,2- dimethylvaleranilide was reacted with tert-butylisocyanate and triethylenediamine to yieldm-(2,2-dimethylvaleramido)phenyl tert-butylcarbamate melting at l24-5 onrecrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in a 100% kill of mustard, flax, lettuce and crabgrass.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in a 100% kill of mustard, flax and lettuce and an 80% kill ofcrabgrass with moderate injury to the surviving plants.

EXAMPLE 55 This examples relates to m-(2-methylhexanamido)- phenylmethylcarbamate. The intermediate 3'- hydroxy-2-methylhexananilide wasprepared by reaction of 2-methylhexanoyl chloride and m-aminophenolusing the procedure of Example 1. Following the procedure described inExample 7, 3'-hydroxy-2- methylhexananilide was reacted with methylisocyanate and triethylamine to yield m-(Z-methylhexanamido)-phenylmethylcarbamate melting at l5960 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in a 100% kill of mustard and flax and 95% kill of lettuce withsevere injury to surviving plants and 95% kill of crabgrass withmoderate damage to the surviving plants. Post-emergence testing of thiscompound at a dosage of 6 pounds per acre resulted in 95%.kill oflettuce and flax with severe damage to the surviving plants and 95% killof mustard with moderate injury to surviving plants; barnyard grass andcarrots were moderately damaged.

EXAMPLE 56 This example relates to m-(3-methyl-2- butenamido)phenylmethylcarbamate. The intermediate 3-hydroxy-3-methyl-2-butenanilide(m.p. l56-7) was prepared from m-aminophenol and 3-methyl-2- butenoylchloride following the procedure described in Example 1 for thepreparation of 3- hydroxy-2-methylvaleranilide. Following the proceduredescribed in Example 7, 3hydroxy-3-methyl-2- butenanilide was reactedwith methyl isocyanate and triethylamine to yieldm-(3-methyl-2-butenamido) phenyl methylcarbamate melting at l68l72 onrecrystallization from aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of flax, 95% kill of mustard with moderate damageto the surviving plants, 95% kill of lettuce with severe injury to thesurviving plants and 60% kill of crabgrass with moderate damage tosurviving plants. Post-emergence testing of this compound at a dosage of6 pounds per acre resulted in 100% kill of mustard, lettuce, flax andcarrots and 90% kill of crabgrass with moderate injury to the survivingplants.

EXAMPLE 57 This example relates to m-acrylamidophenyl methylcarbamate.The intermediate 3'-hydroxyacrylanilide (m.p. l64-5) was prepared fromm-aminophenol and acryloyl chloride preparation of 3'-hydroxy-2-methylvaleranilide. Following the procedure described in Example 7,3'-hydroxyacrylanilide was reacted with methyl isocyanate andtriethylamine to yield macrylamidophenyl methylcarbamate, melting atl778 on recrystallization from ethanol.

Pre-emergence testing of this compound ata dosage of 6 pounds per acreresulted in 100% kill of mustard, flax and lettuce, kill of German haymillet and severe injury to surviving plants, and severe damage tocrabgrass. Postemergence testing of this compound at a dosage of 6pounds per acre resulted in 100% kill of mustard, lettuce, German haymillet, crabgrass and flax.

EXAMPLE 58 This example relates to m-acrylamidophenyl ethylcarbamate.Following the procedure described in Example 7, 3-hydroxyacrylanilidewas reacted with ethyl isocyanate and triethylamine to yieldmacrylamidophenyl ethylcarbamate melting at l645 on recrystallizationfrom aqueous ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce and crabgrass, of German haymillet with the remaining plants of barnyard grass. Post-emergencetesting of this compound at a dosage of 6 pounds per acre resulted inkill of mustard and lettuce, and slight to moderate damage to German haymillet, crabgrass, barnyard grass and flax.

EXAMPLE 59 This example relates to m-acrylamidophenylisopropylcarbamate. Following the procedure described in Example 7, 3'-hydroxyacrylanilide was reacted with isopropyl isocyanate andtriethylamine to yield macrylamidophenyl isopropylcarbamate melting at200-l on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of lettuce, 80% kill of mustard with moderateinjury to the surviving plants and moderate control of German haymillet, crabgrass and flax. Post-emergence testing of this compound at adosage of 6 pounds per acre resulted in 100% kill of lettuce, moderatedamage to flax and mustard, and only slight damage to German hay millet,crabgrass and barnyard grass.

EXAMPLE 60 This example relates to m-acrylamidophenyltertbutylcarbamate. Following the procedure described in Example 18,3'-hydroxyacrylanilide was reacted with tertbutyl isocyanate andtriethylenediamine to yield macrylamidophenyl tertbutylcarbamate meltingat 2045 on recrystallization from ethanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of lettuce, 90% kill of flax, 50% kill of mustardwith remaining plants expected to die, and moderate control of crabgrassand German hay millet; barnyard grass was moderately damaged.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill oflettuce, 75% kill of flax with the remainingplants expected to die and moderate damage to mustard, barnyard grass,German hay millet and crabgrass.

EXAMPLE 61 This example relates to m-(cyclopropylcarbonylamino)phenylmethylcarbamate. the intermediate 3-hydroxy(cyclopropyl)carboxanilide(m.p. l823) was prepared from m-aminophenol and cyclopropylcarbonylchloride following the procedure described in Example l. Following theprocedure described in Example 7, 3'-hydroxy(cyclopropyl)carboxyanilidewas reacted with methyl isocyanate and triethylamine to yieldm-(cyclopropylcarbonylamino) phenyl methylcarbamate melting at 19l2 onrecrystallization from methanol.

Pre-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, lettuce, German hay millet, crabgrass,barnyard grass and flax. Post-emergence testing of this compound at adosage of 6 pounds per acre resulted in 100% kill of lettuce, flax andmustard, 90% kill of crabgrass with moderate injury to the survivingplants and 75% kill of barnyard grass with the remaining plants notexpected to live; German hay millet was so damaged that it was notexpected that the plants would live.

EXAMPLE 62 This example relates to m-(2-methylpropionamido)- phenyldimethylcarbamate. The intermediate maminophenyl dimethylcarbamate wasprepared as follows: m-nitrophenol (100 g) was added gradually to amixture of sodium methoxide (38.8 g) and methanol: the mixture was thenheated at 60 for 2 hours and the methanol evaporated to obtain 120.9 gof the sodium salt of mnitropheno1. Dimethylcarbamoyl chloride (79.0 g)was added dropwise to a suspension of the sodium salt of m-nitrophenol(120 g) in dioxane (600 cc). The reaction mixture was heated at 60-5 fortwo hours and allowed to stir at room temperature overnight. The mixturewas diluted with several volumes of water and the oil was washed severaltimes with H O to obtain 110.5 g of m-nitrophenyl dimethylcarbamatemelting at 55-7. This carbamate was dissolved in ethyl acetate (150 cc),1 g of platinum oxide was added and the mixture reduced on a ParrHydrogenator until hydrogen absorption ceased. The platinum oxide wasremoved by filtration and ethyl acetate was evaporated under reducedpressure to yield S-aminophenyl dimethylcarbamate which melted at8990.5.

lsobutyryl chloride (9.0 g) was added to a solution of m-aminophenyldimethylcarbamate (15.0 g) and triethylamine (8.6 g) in 125 ml ofbenzene maintained at 60. The solution was stirred for 3 hours at 60,then cooled and filtered. The filtrate was cooled to 6 and washed with10% hydrochloric acid and water. The organic layer was dried overmagnesium sulfate, and the solvent was removed in vacuo to give 16.4 gofa cream colored solid. Recrystallization from benzenehexane gave 14.2g of m-(Z-methylpropionamido)phenyl dimethylcarbamate, m.p. 119-l20.

Analysis: Calcd for C H N o C 62.38, H 7.25, N

Found: C 62.67, H 7.45, N 11.15.

Pre-emergence testing of thiscompound at a dosage of 6 pounds per acreresulted in 100% kill of mustard, 90 and 95% kill of German hay millet,crabgrass and flax, respectively, with moderate damage to the survivingplants; barnyard grass and lettuce were moderately damaged.Post-emergence testing of this compound at a dosage of 6 pounds per acreresulted in 100% kill of lettuce and mustard, 80% kill of flax with theremaining plants expected to die; German hay millet, crabgrass andbarnyard grass were moderately damaged.

Other examples of compounds falling within the generic formulaspresented herein, which may be formulated into herbicidal compositionsand applied as herein illustrated are:

m-(Z-Methylhexanamido)phenyl methylcarbamatem-(2,2,4-Trimethylvaleramido)phenyl methylcarbamatem-Z-Pentenamidophenyl methylcarbamate m-Propiolamidophenylmethylcarbamate m-(Z-Methylvaleramido)phenyl diethylcarbamatem-Methacrylamidophenyl isopropylcarbamate m-Methacrylamidophenyltert-butylcarbamate m-Cyclohexanecarboxamidophenyl methylcarbamatem-(4-Methylvaleramido)phenyl methylcarbamate m-Propionamidophenyl2-buten-1-ylcarbamate m-Propionamidophenyl methyl ten-butylcarbamatem-Propionamidophenyl l-chloro-2-propylcarbamate m-Butyramidophenylisobutylcarbamate m-Butyramidophenyl isopropylcarbamatem-Butyramidophenyl tert-buty1carbamate m-Butyramidophenyl2-chloroethylcarbamate m-Butyamidophenyl diethylcarbamatem-Butyramidophenyl methyl tert-butylcarbamate m-lsobutyramidophenylethylcarbamate m-lsobutyramidophenyl 2-chloroethylcarbamatem-Isobutyramidophenyl Z-buten-l-yl carbamate m-lsobutyramidophenyldiethylcarbamate m-Valeramidophenyl propylcarbamate m-Valeramidophenyltert-butylcarbamate m-Valeramidophenyl 2-chloroethylcarbamatem-(2-Methylbutyramido)phenyl propylcarbamate l-chloro-2- 2-buten-1-ylcarbamate m-(2-Methylvaleramido)phenyl 1-chloro-2- propylcarbamatem-Pivalamidophenyl tert-butylcarbamate m-Crotonamidophenyl2-chloroethylcarbamate m-Crotonamidophenyl diethylcarbamatem-Crotonamidophenyl 1-chloro 2-propylcarbamatem-(2-Chloropropionamido)phenyl ethylcarbamatem-(Z-Chloropropionamido)phenyl isopropylcarbamatem-(2-Chloropropionamido)phenyl tertbutylcarbamatem-(2-Chloropropionamido)phenyl isopentylcarbamatem-(2-Chloropropionamido)phenyl 2-chloroethylcarbamatem-(2-Chloropropionamido)phenyl 2-buten-l-yl carbamatem-(2-Chloropropionamido)phenyl diethylcarbamate m-(2,2Dimethylvaleramido)phenyl sec-pentylcarbamate m-(2,2-Dimethylvaleramido)phenyl2-chloroethylcarbamate m-( 2,2-Dimethylvaleramido )phenyl 2-butenl -ylcarbamate m-(2,2-Dimethylvaleramid0)phenyl dimethylcarbamatetertcarbamate m-( 2-Methyl-2-pentenamido)phenyl 2'buten-l -yl carbamatem-(Z-MethyI-Z-pentenamido)phenyl dimethylcarbamate tertm-(Z-Methylcrotonamido )phenyl isopropylcarbamate m-(Z-Methylcrotonamido)phenyl tertbutylcarbamatem-(Z-Methylcrotonamido)phenyl 2-chloroethylcarbamatem-(2-Chloro-2-methylvaleramido)phenyl isopropylcarbamatem-(2Chloro-2-methylvaleramido)phenyl butylcarbamatem-(2-Chl0ro-2-methylvaleramido)phenyl 2-chloroethylcarbamatem-(2-Chloro-2-methylvaleramido)phenyl diethylcarbamatem-(2-Chlorovaleramido)phenyl isopropylcarbamatem-(2-Chlorovaleramido)phenyl tert-butylcarbamatem-(2-Chlorovaleramido)phenyl 2-chloroethylcarbamatem-(Z-Methylhexanamido)phenyl mate m-(Z-Methylhexanamido)phenyldiethylcarbamate m-Z-Methylhexanamido)phenyl tert-butylcarbamatem-(2-Methylhexanamido)phenyl 2-chloroethylcarbamatem-(3,3-Dimethylacrylamido)phenyl ethylcarbamatem-(3,3-Dimethylacrylamido)phenyl dimethylcarbamatem-(3,B-Dimethylacrylamido)phenyl isopropylcarbamatem-(3,3-Dimethylacrylamido)phenyl butylcarbamatem-(3,3-Dimethylacrylamido)phenyl carbamate m-Acrylamidophenyldimethylcarbamate terttert 2-chloroethylisopropylcarbam-Acrylamidophenyl2-chloroethylcarbamate m-(2-Chlorobutyramido)phenyl methylcarbamatem-(2-Chlorobutyramido)phenyl tert-butylcarbamatem-(2-Chlorobutyramido)phenyl dimethylcarbamatem-(2-Chlorobutyamido)phenyl dimethylcarbamate m-(2-Chlor0-2methylpropionamido)phenyl methylcarbamatem-(2-Chlor0-2-methylpropionamido)phenyl ethylcarbamatem-(2-Chloro-2-methylpropionamido)phenyl isopropylcarbamatem-(2-Chloro-2-methylpropionamido)phenyl tertbutylcarbamatem-(2-Chloro-2-methylpropionamido)phenyl 2-chloroethylcarbamatem-(3-Methylbutyramido)phenyl methylcarbamatem-(3-Methylbutyramido)phenyl diethylcarbamatem-(3-Methylbutyramido)phenyl tert-butylcarbamatem-(3-Methylbutyramido)phenyl 2-chloroethylcarbamatem-(2,2-Diethylacetamido)phenyl methylcarbamatem-(2,2-Diethylacetamido)phenyl isopropylcarbamatem-(2,2-Diethylacetamido)phenyl tertbutylcarbamatem-(2,2-diethylacetamido)phenyl 2-chloroethylcarbamatem-Heptanamidophenyl methylcarbamate m-Heptanamidophenyltert-butylcarbamate m-(2-pentenamido)phenyl tert-butylcarbamate It isclear that the classes of m-amidophenyl carbamates described andillustrated herein are characterized by herbicidal activity, and thatthe degree of this activity varies among specific compounds within theseclasses and to some extent among the species of plant to which thesecompounds may be applied. Thus, selection of a specific herbicidalcompound to control undesirable plant species without injury to adesired crop species may readily be made.

Especially good results have been attained by the use ofm-propionamidophenyl 2-chloroethylcarbamate as a postemergence herbicidefor use in controlling weed grasses (barnyard grass, crabgrass) andbroad-leaved weeds (mustard, lambsquartes, pigweed and chickweed) inlegumes (alfalfa, clover, lespedeza, etc.) at a dosage of, for example,one pound per acre.

The active herbicidal compounds of this invention may be formulatedand/or applied with insecticides, fungicides, nematocides, plant growthregulators, fertilizers, and other agricultural chemicals and may beused as effective soil sterilants as well as in herbicidal applications.In applying an active compound of this inven tion, whether formulatedalone or with other agricultural chemicals, an effective amount andconcentration of the m-amidophenyl' N-substituted-carbamate is of courseemployed.

It is apparent that various modifications may be made in the formulationand application of the novel compounds of this invention, withoutdeparting from the inventive concepts herein, as defined in thefollowing claims:

' We claim:

1. Herbicidal compositions comprising as an essential active ingredientan'effective herbicidal amount of a herbicidal compound of the formulawhere R is a hydrogen or lower alkyl and R and R are selected from thegroup consisting of cycloalkyl of 3 to 6 carbon atoms and aliphatichydrocarbon containing up to about 6 catenated carbon atoms which may besubstituted with chlorine or lower alkyl groups and a compatible carriertherefor.

2. Herbicidal compositions as in claim 1 in which R, and R are each analiphatic hydrocarbon radical of up to about 6 catenated carbon atoms.

3. Herbicidal compositions as in claim 1 in which R is hydrogen ormethyl.

4. Herbicidal compositions as in claim 3 in which RA C g is the residueof a carboxylic acid in which the alpha carbon carries a methyl group.

5. Herbicidal compositions as in claim 3 in which R g- H is the residueof a carboxylic acid in which the alpha carbon is part of a cyclopropylring.

6. Herbicidal compositions as in claim 3 in which R, is alkenyl.

7. Herbicidal compositions as in claim 3 in which R, is a l-propenylradical.

8. Herbicidal compositions as in claim 3 in which R,, is ethyl.

9. Herbicidal compositions as in claim 3 in which R,, is Z-methybutyl.

10. Herbicidal compositions as in claim 3 in which R is hydrogen, R ishydrogen, R is t-butyl.

l1. Herbicidal compositions as in claim Sin which R is hydrogen and R isisopropyl.

12. Herbicidal compositions as in claim 8 in which R is hydrogen and Ris sec-butyl.

13. Herbicidal compositions as in claim 8 in which R is hydrogen and Ris Z-chloroethyl.

l4. Herbicidal compositions as in claim 8 in which R is hydrogen and Ris ethyl.

l5. Herbicidal compositions as in claim Sin which R is hydrogen and R ispropyl.

l6. Herbicidal compositions as in claim 3 in which R is hydrogen, R isl-methyl propyl and R is methyl.

17. Herbicidal compositions as in claim 3 in which R is hydrogen, R isl-methylbutyl and R is methyl.

l8. Herbicidal compositions as in claim 3 in which R is hydrogen, R istert-butyl and R is methyl.

19. Herbicidal compositions as in claim 3 in which R is hydrogen, R isl-methylbutyl and R is tert-butyl.

20. Herbicidal compositions as in claim 3 in which R is hydrogen, R isl-methylbutyl and R is isopropyl.

21. Herbicidal compositions as in claim 3 in which R is hydrogen, R isisopropenyl and R is methyl.

22. Herbicidal compositions as in claim 3 in which R is hydrogen, R isl-methyl-l-butenyl and R is methyl.

23. Herbicidal compositions as in claim 3 in which R is chloroethyl.

24. Method of controlling undesired plant growth which comprisesapplying to the locus where control is desired a herbicidal amount of aherbicidal compound of the formula where R is hydrogen or lower alkyland R and R,, are selected from the group consisting of cycloalkyl of 3to 6 carbon atoms and aliphatic hydrocarbon containing up to about 6catenated carbon atoms which may be substituted with chlorine or loweralkyl groups.

25. Method as in claim 24 in which R,, and R are each an aliphaticradical.

26. Method as in claim 25 in which R, and R are each an aliphatichydrocarbon radical of up to about 6 catenated carbon atoms.

27. Method as in claim 26 in which R is hydrogen or methyl and R v-i1 0is the residue of a carboxylic acid in which the alpha carbon carries amethyl group.

28. Method as in claim 26 in which R is hydrogen or methyl and is theresidue of a carboxylic acid in which the alpha carbon carries a methylgroup.

29. Method as in claim 26 in which R is hydrogen or methyl and R isethyl.

30. Method as in claim 29 in which R is hydrogen and R is chloroethyl.

31. Method as in claim 26 in which R is hydrogen or methyl and R ischloroethyl.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,857,693 DATED December 31, 1974 INVENTOR(S) Kenneth L. Hill andKenneth R. Wilson It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 48, "hyxyl" should read "hexyl".

Column 4, line 39', "taxicant" should read "toxicant".

Column 8, line 47, for "phenylisopropylcarbamate" read "phenylisopropylcarbamate" Column 8, line 48, insert the word "the" after"ing".

Column l0, line 22, "bannyard" should read "barnyard".

Column 21, line 19, "5x105, mm, Hg." should read "5xl0-5 mm, Hg."

Column 24, line 20, after "remaining plants" insert "not expected tosurvive, 90% kill of flax and moderate control".

Column 25, line 2, "yanilide" should read "anilide".

Column 25, line 55, after "mustard," insert "95%".

Column 29 claim 10, should read:

"He'rbicidal'compositionsas in claim 3 in which R is hydrogen, R iscyclo ropyl and R is t-butyl."

Signed and Scaled this [sad sixth' D f July 1976 A nest:

RUTH C. MASON Arresrr'ng Officer

1. HERBICIDAL COMPOSITION COMPRISING AS AN ESSENTIALLY ACTIVE INGREDIENTAN EFFECTIVE HERBICIDAL AMOUNT OF A HERBICIDAL COMPOUND OF THE FORMULA2. Herbicidal compositions as in claim 1 in which RA and RB are each analiphatic hydrocarbon radical of up to about 6 catenated carbon atoms.3. Herbicidal compositions as in claim 1 in which RC is hydrogen ormethyl.
 4. Herbicidal compositions as in claim 3 in which
 5. Herbicidalcompositions as in claim 3 in whicH
 6. Herbicidal compositions as inclaim 3 in which RA is alkenyl.
 7. Herbicidal compositions as in claim 3in which RA is a 1-propenyl radical.
 8. Herbicidal compositions as inclaim 3 in which RA is ethyl.
 9. Herbicidal compositions as in claim 3in which RA is 2-methybutyl.
 10. Herbicidal compositions as in claim 3in which RC is hydrogen, RA is hydrogen, RB is t-butyl.
 11. Herbicidalcompositions as in claim 8 in which RC is hydrogen and RB is isopropyl.12. Herbicidal compositions as in claim 8 in which RC is hydrogen and RBis sec-butyl.
 13. Herbicidal compositions as in claim 8 in which RC ishydrogen and RB is 2-chloroethyl.
 14. Herbicidal compositions as inclaim 8 in which RC is hydrogen and RB is ethyl.
 15. Herbicidalcompositions as in claim 8 in which RC is hydrogen and RB is propyl. 16.Herbicidal compositions as in claim 3 in which RC is hydrogen, RA is1-methyl propyl and RB is methyl.
 17. Herbicidal compositions as inclaim 3 in which RC is hydrogen, RA is 1-methylbutyl and RB is methyl.18. Herbicidal compositions as in claim 3 in which RC is hydrogen, RA istert-butyl and RB is methyl.
 19. Herbicidal compositions as in claim 3in which RC is hydrogen, RA is 1-methylbutyl and RB is tert-butyl. 20.Herbicidal compositions as in claim 3 in which RC is hydrogen, RA is1-methylbutyl and RB is isopropyl.
 21. Herbicidal compositions as inclaim 3 in which RC is hydrogen, RA is isopropenyl and RB is methyl. 22.Herbicidal compositions as in claim 3 in which RC is hydrogen, RA is1-methyl-1-butenyl and RB is methyl.
 23. Herbicidal compositions as inclaim 3 in which RB is chloroethyl.
 24. Method of controlling undesiredplant growth which comprises applying to the locus where control isdesired a herbicidal amount of a herbicidal compound of the formula 25.Method as in claim 24 in which RA and RB are each an aliphatic radical.26. Method as in claim 25 in which RA and RB are each an aliphatichydrocarbon radical of up to about 6 catenated carbon atoms.
 27. Methodas in claim 26 in which RC is hydrogen or methyl and
 28. Method as inclaim 26 in which RC is hydrogen or methyl and
 29. Method as in claim 26in which RC is hydrogen or methyl and RA is ethyl.
 30. Method as inclaim 29 in which RC is hydrogen and RB is chloroethyl.
 31. Method as inclaim 26 in which RC is hydrogen or methyl and RB is chloroethyl.